Oxo synthesis followed by hydrogenation to alcohols



Patented Mar. 14, 1950 OX SYNTHESIS FOLLOWED BY HYDRO- GENATION TO ALCOHOLS Robert E. Schexnailder, Jr., Baton Rouge, La.,

assignor to Standard Oil Development Company, a corporation of Delaware No Drawing.

Original application October 31,

1946, Serial No. 707,033. Divided and this ap-- plication January 23, 1948, Serial No. 4,059

6 Claims.

This application is a division of my copending application, Serial No. 707,033 filed October 31, 1946.

The present invention is concerned with improved catalysts. The invention is more particularly directed to catalysts comprising silica which are suitable for oxo-synthesis reactions. In accordance with my invention improved oxo-synthesis catalysts are prepared by impregnating a gel comprising silica with salts of cobalt, thorium and copper and then decomposing these salts on the silica.

It is well known in the art to conduct hydrocarbon synthesis reactions by contacting hydro gen and oxides of carbon with catalysts under various temperature and pressure conditions. The

catalyst employed is usually selected from the iron group metals, as for example, iron cobalt and nickel. The catalysts are utilized either alone or are employed in conjunction with carriers, such as kieselguhr, diatomaceous earth, synthetic gels, silica and alumina. Promoters, such as oxides of sodium, potassium, chromium, zinc, aluminum, magnesium, and the rare earth metals are used with the iron group metals. These catalysts are employed in'either fixed bed or fluid catalyst operations.

The temperatures employed in the synthesis reaction vary widely, as for example, in the range from about 300 F. to about 800 F. and are generally in the range from about 350 F. to about 700 F. The pressures, likewise vary considerably and are a function of other operating conditions, such as catalyst employed, activity of the catalyst, character of the feed gases and the temperature utilized. Pressures in the range from about 1 to 100 and higher atmospheres have been suggested. The character of the feed gases introduced into the synthesis reaction zone depends somewhat on the particular temperatures and premures, and upon the catalyst employed. For example, when employing cobalt type catalyst, it is preferred to use about 1 mol of carbon monoxide to about 2 mols of hydrogen, while when an iron type catalyst is utilized, equal mols of hydrogen and carbon monoxide in the feed synthesis gases are desirable.

The synthesis gases comprising hydrogen and carbon monoxide are produced by various procedures. Methane or natural gas may be oxidized with a reducible metal oxide or with pure oxygen. Other feed stocks may comprise coal, shale and other hydrocarbons. The reaction may be conducted in a single or in a plurality of stages. One procedure is to employ a two-stage reform- 2 ing process using steam and carbon dioxide. When employing methane as a feed gas and reducing the same with a reducible metal oxide, the reactions are generally conducted at temperatures in the range from about 1400 F. to about 2000 F.

It has, heretofore, been known in the art to contact gases and solids by passing the gases upwardly through an enlarged treating zone, containing a body of finely divided solids to be contacted, at a controlled velocity to maintain the solids in the treating zone in a. quasi-liquid like state. Under properly controlled conditions, the subdivided solid particles are not only maintained in a highly turbulent, quasi-liquid and ebullient state, but there exists a rapid and overall circulation of the fluidized solids throughout the fluid bed.

Processes of this character, wherein fluidized solids are contacted with gases, have a number of inherent and important advantages. For example, intimate contact between the gases and the fluid subdivided solids is secured. It is also possible to maintain a substantially uniform temperature throughout the bed as a result of the extremely rapid transfer of heat from one section of the bed to the other because of the rapid circulation of the fluid subdivided solids. Furthermore, due to the rapid transfer of heat between the solids under these conditions, it is possible to readily add or extract heat from the mass at an extremely rapid rate.

In fluid operations catalyst particles generally com-prise particles having a micron size in the range from about 20 to 200 microns and higher. These particles are suspended in a fluid ebullient state by means of an upflowing suspending gas, the velocity of which is in the range from about 0.1 to 5.0 and higher feet per second.

In hydrocarbon synthesis reactions as discussed heretofore, it is known to add olefins with the feed gases comprising carbon monoxide and hydrogen in order to secure production of oxygenated compounds in accordance with the 0x0- synthesis reaction. The oxo-synthesis reaction involves reacting olefins with a mixture of carbon monoxide and hydrogen in the presence oi. a cobalt containing catalyst or an equivalent catalyst to form an aldehyde which is usually hydrogenated to the corresponding alcohol. The ratio of hydrogen to carbon monoxide may vary appreciably. Ratios of 0.5 volume of hydrogen to 4.0 volumes of hydrogen per volume or carbon monoxide are employed. The preferred ratios comprise about 1.0 volume of hydrogen per volume of 3 carbon monoxide. Tha quantities of olefins employed per volume of synthesis gas likewise vary considerably, as well as the composition of the olefin feed stream. The oxo-synthesis reaction is generally conducted employing a pressure in the range o'f about 100 to 300 atmospheres and a temperature in the range of about 200 1. to 400 I". r

In the hydrogenation step, any catalyst as, for example, nickel, tungsten, or sulfides of group VI and group VIII metals of the periodic table may be utilized. The hydrogenation temperatures are generally in the range from about 150 F. to 450 1''. while the pressures are usually in the range of about 100 to 300 atmospheres. The quantity of synthesis gas with respect to'oleflns utilized may vary considerably as, for example, from 1000 to 45,000 cu. ft. of carbon monoxide and hydrogen per barrel of olefin feed. In general, approximately 2,500 to 15,000 cu. it. of synthesis gas per barrel of olefin feed is employed.

I have, however, discovered an improved catalyst and the method for manufacturin the same which will produce superior results in an oxo-synthesis reaction. In accordance with my invention a hydrogel comprising silica is impregnated with salts of cobalt, thorium and copper. The salts are subsequently decomposed to give a catalyst of superior quality. The silica hydrogel may be prepared by any suitable method. One method is to prepare the silica hydrogel by mixing an alkali silicate with an acid. The alkali silicate usually comprises a sodium silicate (Na:O.3.25SiO:) solut'ion having a specific gravity of about 1.2. This is mixed with a sulfuric acid having a specific gravity somewhere in the range of about 1.19. The hydrosol may be impregnated with a soluble salt of the desired metal or the hydrosol may be allowed to gel and the resulting hydrogel washed and soaked in a solution comprising the salt of the desired metal or metals.

Another method which may be employed for the preparation of the silica hydrogel is to mix sulfuric acid with an alkali metal silicate. The silica hydrosol is treated with magnesia under conditions to form the silica hydrogel and mag nesia sulfate. The magnesia is removed by washing with water. The resulting silica hydrogel is impregnated with any suitable salt of cobalt, thorium and copper. As pointed out heretofore, the silica hydrosol may be impregnated, before treating with the magnesia, with the salts of cobalt, thorium and copper. The process of my invention may be readily understood by reference to the following examples illustrating the same.

Example 1 A sodium silicate (Na2O.3.25Sl02) solution having a specific gravity 1.2 was prepared. This solution was mixed with a sulfuric acid solution having a specific gravity somewhere in the range of about 1.19. The hydrogel was washed and mixed with nitrates of cobalt, thorium and copper. The mixing was made by mulling the silica hydrogel with the nitrates. The plasticized mass was heated to a temperature of 550 F. to decompose the nitrates to the metallic oxides. The catalyst was activated at a temperature of about 850 F.

The catalyst comprised 62% silica, 32% cobalt, thoria and 1% copp r.

Example 2 The catalyst prepared in accordance with Example 1 was employed in a synthesis zone operating at a temperature of about 275 F. and at a pressure of about 3,000 pounds per square inch. The feed comprised di-isobutylene, hydrogen and carbon monoxide. The feed rate of di-isobutylene as compared to hydrogen and carbon monoxide was about 1.6 mols of di-isobutylene to 1 mol of hydrogen and 1 mol of carbon monoxide.

Example 3 A catalyst prepared in accordance with Example l was used to contact olefins, hydrogen and carbon monoxide in a synthesis reaction zone. The results of the operation were as follows:

Catalyst reduction temperature, F 700 H: rate, v./v./hr 4000 Wt. per cent catalyst on olefin feed l3 Feed di-isobutylene Oxo operation:

Hours of run 5 Temperature, F 275 Pressure, p. s. i. g 3000 Hydrogenation operation:

Hours of run 12 Temperature, F 350 Pressure, p. s. Lg 2500 Liquid product inspections:

Hydroxyl No 286 Carbonyl No 9 Saponification No 7 Acid No 1.3 Recovery, wt. per cent (on liquid feed plus catalyst) 121 Conversion, per cent 87 My invention comprises treating mixtures comprising olefins, hydrogen and carbon monoxide with a silica hydrogel catalyst impregnated with cobalt, thorium and copper. In general, I prefer the percentage of silica. to be in the range from about 15 to preferably about 60%. I pre- 'fer that the cobalt concentration be in the range of 20 to 40%. preferably about 30%. The concentration of thoria is preferably 3 to 8%. The concentration of the copper, I prefer to be in the range below about 5%, preferably in the range from 1 to 3%.

The silica hydrosol may be impregnated before the formation of the hydrogel or the hydrogel may be impregnated after it is formed. Any suitable means may be employed to decompose the salts of cobalt, thorium and copper. In general, the salts are decomposed by subjecting the hydrogel to a heat treatment from about 1 to 6 hours at a temperature in the range from about 400 to 600 F. I then prefer to activate the impregnated silica hydrogel at a temperature in the range of about 800 F. to 1200" F. Any suitable salts may be used, as for example, the nitrates, the sulfates or the chlorates. However, I prefer to employ decomposable salts as for example, the nitrates.

The process of my invention is not to be limited by any theory as to mode of operation but only in and by the following claims.

I claim:

1. In a .carbonylation process wherein olefins and about equimolar amounts of carbon monoxide and hydrogen are contacted in a liquid phase with a carbonylation catalyst in a carbonvlation zone under pressures of 100 to 300 atmospheres and temperatures of 200 to 400 R. to produce oxygenated organic reaction products comprising aldehydes containing one more carbon atom per molecule than said olefins and wherein the products from said initial stage are subsequently hydrogenated under pressures of from 100 to 300 atmospheres in a second stage to form alcohols, the improvement which comprisesemploying as a carbonylation catalyst in said initial stage, a catalyst consisting essentially of silica hydrogel impregnated with cobalt, thoria and copper.

2. The process of claim 1 in which said catalyst comprises about 62% silica, 32% cobalt, 5% thoria and 1% copper.

3. The process of claim 1 wherein said olefin is di-isobutylene.

4. The process of claim 1 wherein said catalyst is prepared by impregnating a silica hydrogel with decomposable salts of cobalt, thoria, and copper, said salts being decomposed on said silica hydrogel, and further activting said catalyst by heating at an elevated temperature.

5. The process of claim 4 wherein said salts comprise cobalt nitrate, thorium nitrate, and copper nitrate.

6. The process of claim 4 wherein said catalyst is activated at a temperature in the range of about 800 to 1200 F.

ROBERT E. SCHEEIAILDER, JR.

6 REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES U. S. Naval Technical Mission in Europe. The Synthesis of Hydrocarbons and Chemistry from C0 and H2," page 120, Sept. 1945. Listed in bibliograph of Scientific and Industrial Reports, Dept. of Commerce, OTS, vol. 2, No. 5, page 321, Aug. 2, 1946. 

1. IN A CARBONYLATION PROCESS WHEREIN OLEFINS AND ABOUT EQUIMOLAR AMOUNTS OF CARBON MONOXIDE AND HYDROGEN ARE CONTACTED IN A LIQUID PHASE WITH A CARBONYLATION CATALYST IN A CARBONYLATION ZONE UNDER PRESSURES OF 100 TO 300 ATMOSPHERES AND TEMPERATURES OF 200* TO 400*F., TO PRODUCE OXYGENATED ORGANIC REACTION PRODUCTS COMPRISING ALDEHYDES CONTAINING ONE MORE CARBON ATOM PER MOLECULE THAN SAID OLEFINS AND WHEREIN THE PRODUCTS FROM SAID INITIAL STAGE ARE SUBSEQUENTLY HYDROGENATED UNDER PRESSURES OF FROM 100 TO 300 ATMOSPHERES IN A SECOND STAGE TO FORM ALCOHOLS, THE IMPROVEMENT WHICH COMPRISES EMPLOYING AS A CARBONYLATION CATALYST IN SAID INITIAL STAGE, A CATALYST CONSISTING ESSENTIALLY OF SILICA HYDROGEL IMPREGNATED WITH COBALT, THORIA AND COPPER. 